EP0228121B1 - Preparation of nonionic surfactants - Google Patents
Preparation of nonionic surfactants Download PDFInfo
- Publication number
- EP0228121B1 EP0228121B1 EP86202215A EP86202215A EP0228121B1 EP 0228121 B1 EP0228121 B1 EP 0228121B1 EP 86202215 A EP86202215 A EP 86202215A EP 86202215 A EP86202215 A EP 86202215A EP 0228121 B1 EP0228121 B1 EP 0228121B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- alkanol
- process according
- group
- aluminium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000002736 nonionic surfactant Substances 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims description 68
- 239000000376 reactant Substances 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 51
- 125000002947 alkylene group Chemical group 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 31
- -1 alkyl sulphuric acids Chemical class 0.000 claims description 26
- 235000011149 sulphuric acid Nutrition 0.000 claims description 25
- 238000009826 distribution Methods 0.000 claims description 23
- 150000007513 acids Chemical class 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000001117 sulphuric acid Substances 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 15
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 150000001399 aluminium compounds Chemical class 0.000 claims description 8
- 201000006747 infectious mononucleosis Diseases 0.000 claims description 7
- 229940077746 antacid containing aluminium compound Drugs 0.000 claims description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 3
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229950000244 sulfanilic acid Drugs 0.000 claims description 3
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical class [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 claims description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 description 52
- 239000000203 mixture Substances 0.000 description 48
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 238000007046 ethoxylation reaction Methods 0.000 description 10
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 150000004703 alkoxides Chemical class 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- OIPMQULDKWSNGX-UHFFFAOYSA-N bis[[ethoxy(oxo)phosphaniumyl]oxy]alumanyloxy-ethoxy-oxophosphanium Chemical compound [Al+3].CCO[P+]([O-])=O.CCO[P+]([O-])=O.CCO[P+]([O-])=O OIPMQULDKWSNGX-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 150000004707 phenolate Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000001164 aluminium sulphate Substances 0.000 description 2
- 235000011128 aluminium sulphate Nutrition 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- IULJSGIJJZZUMF-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC=C1S(O)(=O)=O IULJSGIJJZZUMF-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- MKUXAQIIEYXACX-UHFFFAOYSA-N aciclovir Chemical compound N1C(N)=NC(=O)C2=C1N(COCCO)C=N2 MKUXAQIIEYXACX-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- ZHGASCUQXLPSDT-UHFFFAOYSA-N cyclohexanesulfonic acid Chemical compound OS(=O)(=O)C1CCCCC1 ZHGASCUQXLPSDT-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- SSILHZFTFWOUJR-UHFFFAOYSA-N hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCS(O)(=O)=O SSILHZFTFWOUJR-UHFFFAOYSA-N 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
Definitions
- This invention relates to a process for the preparation of an alkanol alkoxylate product having a narrow-range alkylene oxide adduct distribution and a low content of residual alkanol.
- a large variety of products useful, for instance, as nonionic surfactants, wetting and emulsifying agents, solvents, and chemical intermediates, are prepared by the addition reaction (alkoxylation reaction) of alkylene oxides withorganic compounds having one or more active hydrogen atoms.
- alkoxylation reaction alkoxylation reaction
- alkanol ethoxylates and alkyl-substituted phenol ethoxylates prepared by the reaction of ethylene oxide with aliphatic alcohols or substituted phenols of about 6 to 30 carbon atoms.
- Such ethoxylates, and to a lesser extent corresponding propoxylates and compounds containing mixed oxyethylene and oxypropylene groups are most commonly applied as nonionic detergent components of commercial cleaning formulations for use in industry and in the home.
- alkylene oxides to alkanols and other active-hydrogen containing compounds is known to be desirably promoted by a catalyst, most conventionally a catalyst of either strongly acidic or strongly basic character.
- suitable basic catalysts are the basic salts of the alkali metals of Group I of the Periodic Table, e.g., sodium, potassium, rubidium, and cesium, and the basic salts of certain of the alkaline earth metals of Group II of the Periodic Table, e.g., calcium, strontium, barium and in some cases magnesium.
- Conventional acidic alkoxylation catalysts include, broadly, the Lewis acid or Friedel-Crafts catalysts.
- catalysts are the fluorides, chlorides, and bromides of boron, antimony, tungsten, iron, nickel, zinc, tin, aluminium, titanium and molybdenum.
- fluorides, chlorides, and bromides of boron, antimony, tungsten, iron, nickel, zinc, tin, aluminium, titanium and molybdenum are also reported.
- acidic alkoxylation catalysts are sulphuric and phosphoric acids; perchloric acid and the perchlorates of magnesium, calcium, manganese, nickel and zinc; metal oxalates, sulphates, phosphates, carboxylates and acetates; alkali metal fluoroborates, zinc titanate; and metal salts of benzene sulphonic acid.
- Alkylene oxide addition reactions are known to produce a product mixture of various alkoxylate molecules having different numbers of alkylene oxide adducts (oxyalkylene adducts), e.g., having different values for the adduct number n in formula III above.
- the adduct number is a factor which in many respects controls the properties of the alkoxylate molecule, and efforts are made to tailor the average adduct number of a product and/or the distribution of adduct numbers within a product to the product's intended service.
- Characteristic of the product of the typical acid-catalyzed alkoxylation is a statistical Poisson distribution in which the relative concentration of each individual alkoxylate species may be expressed in terms of the following equation, which is well known to those in the oligomerization and polymerization arts: wherein N represents the overall molar ratio of reactant alkylene oxide to reactant alkanol, n represents alkylene oxide adduct number, P(n) represents the mole percent of alkoxylate product molecules having the adduct number n, and e indicates the natural logarithm function. In effect, this expression reflects a reaction mechanism under which all hydroxyl-containing species in the alkoxylation reaction mixture (i.e., both alkanol reactant and alkoxylate intermediates) react with the alkylene oxide at the same rate.
- acid catalysis provides a relatively narrow distribution product, it is known to have substantial disadvantage in several other respects.
- the acids are often unstable with limited life and effectiveness as catalysts in the alkoxylation mixture.
- Both the acid catalysts themselves and their decomposition products catalyze side reactions producing relatively large amounts of polyalkylene glycols, and also react directly with the components of the alkoxylation mixture to yield undesirable, and often unacceptable, by-products such as organic derivatives of the acid.
- the invention as defined in the claims, relates to a process for the preparation of an alkanol alkoxylate product having a narrow-range alkylene oxide adduct distribution and a low content of residual alkanol, which is characterised by reacting an alkylene oxide reactant comprising one or more C 2 to C 4 vicinal alkylene oxides with an alkanol reactant comprising one or more C 6 to C 30 alkanols in the presence of a catalytically effective amount of a catalyst prepared by contacting (i) one or more sulphur-containing acids selected from the group consisting of sulphur trioxide, sulphuric acid, alkyl sulphuric acids, sulphurous acids, and organic and inorganic sulphonic acids and (ii) one or more aluminium compounds selected from the group consisting of aluminium alcoholates and aluminium phenolates.
- aluminium alcoholate and/or phenolate compounds can be applied per se, i.e., added directly to the process mixture, or, alternatively, can be formed in situ in the alcohol-containing process mixture by introduction of suitable precursors capable of conversion to aluminium alcoholate and/or phenolate compound(s), which in turn function as a catalyst component or as a precursor to the desired catalyst.
- the process of the invention yields (1) a higher quality product relatively free of by-products, (2) a product having a narrower distribution of alkylene oxide adducts, and (3) a product having a reduced level of residual alkanol.
- the invention is applied to processes utilizing an alkylene oxide (epoxide) reactant which comprises one or more C 2 to C 4 vicinal alkylene oxides.
- alkylene oxide epoxide
- Reactants which comprise ethylene oxide, propylene oxide, or mixtures of ethylene oxide and propylene oxide are preferred, while reactants wherein the alkylene oxide content consists essentially of ethylene oxide are considered particularly preferred.
- the alkanol reactant very suitably comprises one or more alkanols having carbon number in the range from 6 to 30.
- An alkanol reactant consisting essentially of primary, mono-hydric alkanols is considered most preferred, although secondary and tertiary alcohols as well as polyhydric alkanols are also very suitably utilized in the process of the invention either alone or in mixtures with the primary mono-hydric alkanols.
- the alkanol reactant consists essentially of one or more C 6 to C 30 primary mono-hydric alkanols.
- the carbon chains of the alkanols may be of either branched or linear (straight chain) structure, although preference further exists for alkanol reactants in which greater than about 50 per cent, more preferably greater than about 70 per cent and most preferably greater than about 90 per cent of the molecules are of linear (straight-chain) carbon structure.
- such preferences relate more to the utility and value of the product alkoxylates in commercial services than to the operability or performance of the process of the invention.
- the alkylene oxide reactant and the active hydrogen reactant are necessarily contacted in the presence of the specified two-component catalyst.
- the process of the invention makes use of one or more sulphur-containing acids sclected from sulphur trioxide (S0 3 ) and acids of the class represented by the empirical formula ZSO 3 H. Included within this class are sulphuric acid (with Z in the formula representing -OH), monoalkyl esters of sulphuric acid which are also commonly called alkyl sulphuric acids (with Z representing an alkoxy group), sulphurous acid (wherein Z represents H), and sulphonic acids wherein Z represents a univalent inorganic atom or organic radical.
- Preferred alkyl sulphuric acids include those with an alkoxy group of about 1 to 30 carbon atoms. Alkyl sulphuric acids having an alkoxy group of about 1 to 20 carbon atoms are more preferred, while those having an alkoxy group of about 8 to 20 carbon atoms are considered most preferred.
- Suitable inorganic sulphonic acids include chlorosulphonic acid (wherein Z is CI), fluorosulphonic acid-(wherein Z is F) and sulphamic acid (wherein Z is NH 2 ).
- Suitable organic sulphonic acids include the alkane- and cycloalkane sulphonic acids, as well as arenesulphonic acids and heterocyclic sulphonic acids.
- Specific examples of the alkane sulphonic acids include methanesulphonic acid, ethanesulphonic acid, propanesulphonic acid, butanesulphonic acid, pen- tanesulphonic acid, hexanesulphonic acid, dodecanesulphonic acid, hexadecanesulphonic acid, trifluoromethane sulphonic acid, sulphosuccinic acic, and cyclohexylsulphonic acid.
- arenesulphonic acids include benzenesulphonic acid, toluenesulphonic acid, styrene-(i.e., vinyl benzene) sulphonic acid, 5-sulphosalicylic acid, phenolsulphonic acid, and 1,6-napthalene disulphonic acid.
- heterocyclic sulphonic acids include sulphanilic acid. Alkyl and aryl groups of the sulphonic acid molecule are suitable substituted with relatively inert organic and/or inorganic substituents. Examples of substituted organic sulphonic acids include 4-hydroxybenzoic acid, trifluoromethane sulphonic acid, isethionic acid, and taurine.
- the sulphur-containing catalyst component is suitably introduced directly to the process mixture or formed therein upon addition to the mixture of precursors of the sulphur-containing acid(s). Mixtures of sulphur-containing acids are very suitable.
- a particularly preferred group of sulphur-containing acids is that which consists of sulphuric acid, sulphur trioxide, C 1 to C 30 alkyl sulphuric acids, sulphanilic acid, toluenesulphonic acid, styrenesulphonic acid, methanesulphonic acid, and 5-sulphosalicylic acid.
- a catalyst component selected from the group consisting of sulphuric acid, sulphur trioxide, and the C 1 to C 30 alkyl sulphuric acids is considered more preferred, and sulphuric acid is considered most preferred, for use in the invention from the standpoint of overall process performance and economics, and of product quality.
- the second necessary component of the catalyst of the process of the invention suitably comprises one or more aluminium alcoholate ore phenolate compounds.
- this component comprises one or more alkoxide or phenoxide compounds of the formula
- At least one of X 1 , X 2 , and X3 represents an -OR group, wherein the R substituent is selected from the group consisting of alkyl and optionally alkyl-substituted phenyl groups, preferably C 1 to C 30 alkyl and optionally substituted phenyl groups.
- the X i , X 2 , and X 3 substituents which represent -OR groups suitably represent the same or different -OR groups.
- the invention encompass embodiments utilizing aluminium compounds in which at least one of X l , X 2 and X 3 represents a precursor group which undergoes conversion to an -OR group in the process mixture, and particularly in the presence of the alkanol reactant.
- groups which serve as precursors include halogen atoms, particularly chlorine and bromine atoms, carboxy (for instance acetate) groups, and alkyl (for instance methyl) groups.
- the one or more of X l , X 2 , and X 3 which are not either -OR groups or precursors for the formation of -OR groups suitably represent organic or inorganic groups which are substantially inert in the process medium.
- Xi and X2 and X 3 all represent (or are in practice converted to) the same or different -OR groups.
- preferred alkoxide compounds suitable as catalyst components for purposes of the invention include the aluminium alkoxides (wherein R is C 1 to C 30 alkyl), including the lower alkoxides, e.g., aluminium ethoxide, aluminium isopropoxide, and aluminium t-butoxide, as well as the higher alkoxides having one or more of their alkyl R substituents in the same Ca to C 20 range as the alkanol reactant of the process, e.g., nonyl, decyl, dodecyl, and hexadecyl groups.
- R is C 1 to C 30 alkyl
- the lower alkoxides e.g., aluminium ethoxide, aluminium isopropoxide, and aluminium t-butoxide
- the higher alkoxides having one or more of their alkyl R substituents in the same Ca to C 20 range as the alkanol reactant of the process e.g., non
- preferred phenoxide compounds useful in this service include aluminium phenoxide, lower alkyl-substituted phenol derivatives such as aluminium benzyloxide and higher alkyl-substituted phenol derivatives, e.g., compounds wherein R represents nonylphenyl, tridecylphenyl, pentadecylphenyl, etc.
- preferred compounds which serve as precursors for the formation in situ of aluminium alkoxide compounds include aluminium triacetate and trialkylaluminium compounds such as trimethylaluminium and triethylaluminium.
- each of the X l , X 2 , and X 3 substituents is an -OR group wherein R is an alkyl group having a carbon number in the range from 1 to 30, more preferably a carbon number in the range from 1 to 20, and most preferably a carbon number which corresponds to the carbon number(s) of the particular alkanol reactant employed in the given process application.
- R is an alkyl group having a carbon number in the range from 1 to 30, more preferably a carbon number in the range from 1 to 20, and most preferably a carbon number which corresponds to the carbon number(s) of the particular alkanol reactant employed in the given process application.
- the reaction of a dodecyl alcohol reactant is most preferably conducted in the presence of a catalyst which comprises a catalyst in which a substantial portion of the second catalyst component is a compound of the formula Al-(OR) 3 , wherein each R is a dodecyl group.
- an aluminium isopropoxide catalyst component is contacted with a higher alkanol alkoxylation reactant (e.g., a G2 to C 15 alkanol mixture) a transalcoholysis reaction results which liberates isopropanol and converts at least a portion of the aluminium isopropoxide to aluminium alkoxides having C n to C 15 alkyl substituents.
- a higher alkanol alkoxylation reactant e.g., a G2 to C 15 alkanol mixture
- a lower carbon number aluminium alkoxide e.g., an alkoxide characterized by alkyl group carbon number(s) of less than about 6
- alkanol reactant e.g., an alkoxide characterized by alkyl group carbon number(s) of less than about 6
- the catalyst components are preferably applied in a molar ratio of the first sulphur-containing acid component to the second aluminium containing component that is in the range from 0.1:1 to 2:1. Higher relative ratios result in lower reaction rates and higher degrees of by-product formation, while at lower ratios the reaction rate is undesirably low. Molar ratios of the first catalyst component to its second component in the range from 0.3:1 to 1:1 are more preferred, while molar ratios between 0.4:1 and 0.6:1 are considered most preferred.
- the catalyst combination is present in the reaction mixture in a catalytically effective amount.
- a quantity of catalyst is desirably at least about 0.01 %w (per cent by weight) of the combined total of the two components relative to the alkanol reactant.
- catalyst quantity is not narrowly critical, preference may be expressed for use of the catalyst in amount of at least about 0.05 %w, while an amount between 0.1 and 1 %w is considered most preferred. Substantially greater quantities of catalyst, e.g., up to 10 %w, are also very suitable.
- the alkoxylation reaction in the invention may be conducted in a generally conventional manner.
- the catalyst components may initially be mixed with the alkanol reactant.
- a substantially liquid mixture forms, although it is not necessary that all of the added catalyst dissolve in the alkanol.
- This mixture is then contacted, preferably under agitation, with alkylene oxide reactant, which is typically introduced in gaseous form.
- the order in which the catalyst components and the reactants are contacted has not been found to be critically important to the invention.
- the observation of a reaction between the two catalyst components when they are pre-mixed in the absence of alcohol and ethylene oxide suggests that the two specified components may in fact serve as precursors of a single effective catalyst which has not been otherwise identified. Accordingly, the catalyst is described with reference to a combination of, or, equivalently, to a catalyst prepared by contacting the two specified components.
- the two reactants are utilized in quantities which are predetermined to yield an alkoxylate product of the desired mean or average adduct number, e.g., typically from less than one to about 30.
- suitable and preferred process temperatures are from 70 ° C to 200 °C and pressures above atmospheric pressure are preferred.
- a temperature of at least about 70 ° C, particularly at least 100 ° C, is typically preferred for a significant rate of reaction, while a temperature less than 200 ° C, particularly less than 180 ° C, and most particularly less than 170 ° C, is typically desirable to minimize degradation of the product.
- the two-component catalyst used in the invention is highly active, and care must be taken to control the temperature of the exothermic reaction.
- Superatmospheric pressures e.g., pressures between 0.7 and 11 bar (gauge) are preferred. While these procedures describe a batch mode of operation, the invention is equally applicable to a continuous process.
- the alkanol reactant is generally a liquid and the alkylene oxide reactant is generally a vapour for such reactions.
- Alkoxylation is then suitably conducted by introducing gaseous alkylene oxide into a pressure reactor containing the liquid alkanol and the two components of the catalyst combination.
- the partial pressure of the lower alkylene oxide reactant is preferably limited, for instance, to less than about 4 bar and/or the reactant is preferably diluted with an inert gas such as nitrogen, for instance, to a vapour phase concentration of about 50 per cent or less.
- the reaction can, however, be safely accomplished at greater alkylene oxide concentration, greater total pressure and greater partial pressure of alkylene oxide if suitable precautions, known to the art, are taken to manage the risks of explosion.
- the product is preferably neutralized to deactivate the catalyst.
- Neutralization is suitably accomplished by the addition of a base such as sodium or potassium hydroxide to the acidic product mixture.
- Neutralized catalyst residues are very suitably left in the product, or may be removed if desired, for example, by precipitation or extraction or the like.
- the alkoxylate prepared in the process of the invention is typically a product of very acceptable quality, having a relatively low content of polyalkylene glycols and other by-products, as well as a low content of residual alkanol reactant.
- the content of residual alkanol will vary from one alkoxylation product to another, and is dependent upon the degree of alkoxylation, i.e., the average alkylene oxide adduct number
- the residual alkanol content of a product prepared according to the invention and having a given average adduct number is less than the content of residual alkanol in a product of like average adduct number which has been prepared according to conventional acid-catalyzed alkoxylation.
- the alkylene oxide reactant consisted of ethylene oxide and the alkanol reactant was a NEODOL 23 Alcohol (trademark of Shell Chemical Company) characterized as a mixture of primary, 80% linear (20% branched) alkanols having twelve and thirteen carbon atoms (about 40% by mole C 12 and 60% by mole C 13 ).
- the liquid alkanol reactant was dried to a water content of about 40 ppm (as indicated by Karl Fischer water analysis) by sparging with nitrogen at 130 ° C for one hour.
- the product was analyzed by GC-LC techniques to determine the mean average adduct number of the ethoxylate, the ethylene oxide adduct distribution of the ethoxylate, the content of residual alkanol reactant in the product, and the quantity of polyethylene glycol by-products formed.
- Example 1 followed the general procedures outlined above, utilizing aluminium isopropoxide (AI(OR) 3 , where R is isopropyl) as the first catalyst component and concentrated (96%) sulphuric acid as the second catalyst component.
- AI(OR) 3 aluminium isopropoxide
- sulphuric acid concentrated (96%) sulphuric acid
- the alkanol ethoxylate product was found to have a mean average adduct number of 2.0 and to contain 4.4 %w of residual alkanol reactant.
- the product also contained 0.6 %w polyethylene glycols (PEG).
- the ethylene oxide adduct distribution of the product is presented in Table I and compared with that of (1) an ethoxylate of equivalent mean adduct number which was produced using a conven tional potassium hydroxide catalyst and (2) with a (calculated) Poisson distribution as is characteristic of conventional acid-catalyzed ethoxylation reactions.
- the distribution is substantially more narrow than that which is characteristic of conventional base-catalyzed ethoxylation reactions, including those catalyzed by compounds of sodium or potassium or other Group I metals as well as those catalyzed by compounds of barium or other Group II metals.
- the distribution is more narrow than that obtained using conventional acid catalysts such as sulphuric acid.
- Example 2 the general procedures were again followed as in Example 1, with the addition of separate processing step for the conversion of substantially all of the aluminium isopropoxide to an aluminium alkoxide of the C J2 and C 13 alkanols.
- the second (sulphuric acid) catalyst component was added to the 150 grams of the dried alkanol reactant, and before the transfer of the alkanol/catalyst mixture to the autoclave, the mixture was heated to 130 ° C and maintained at this temperature under a nitrogen sparge for two hours. Under these conditions, a transalcoholysis reaction occurred between the aluminium isopropoxide and the C 12 and C 13 alkanols. Isopropanol released by alcoholysis was removed from the system by the nitrogen sparge. Following the transalcoholysis, the mixture was cooled to 30 ° C and transferred to the autoclave under nitrogen atmosphere.
- An alkoxylation process according to the invention was carried out using aluminium t-butoxide (AI(OR) 3 , where R is t-butyl) as the first catalyst component.
- AI(OR) 3 aluminium t-butoxide
- R is t-butyl
- this Example 3 about 5.0 grams (0.02 moles) of aluminium t-butoxide was dissolved in about 300 grams (1.55 moles) of the dried alkanol reactant at 100 ° C. The mixture was cooled to 30 ° C and about 1.0 gram (0.01 moles) of concentrated sulphuric acid was added, producing a slightly hazy, colourless solution. The general procedure was then again followed for the ethoxylation reaction.
- An alkoxylation process according to the invention was conducted using a catalyst which contained the two catalyst components in a molar ratio of 1:1, i.e., one part of the first component (aluminium isopropoxide) and one part of the second component (concentrated sulphuric acid).
- aluminium isopropoxide aluminium isopropoxide
- concentration sulphuric acid aluminium isopropoxide
- about 1.1 grams (0.005 moles) of the first component was dissolved in 150 grams of the predried alkanol reactant at 100 ° C. The mixture was then cooled to 30 ° C, and about 0.5 grams (0.005 moles) of the sulphuric acid was added.
- the product had a mean average adduct number of 2.0, and contained 4.4 %w residual alkanol and 2.1 %w PEG.
- Example 5 sulphur trioxide was utilized as the second catalyst component. About 2.7 grams (0.013 moles) of aluminium isopropoxide was dissolved in the 150 grams of alkanol reactant at 100 °C. The mixture was cooled to 30 ° C, and 1.06 grams (0.013 moles) of sulphur trioxide was added.
- Alkoxylate product had a mean average adduct number of 2.3, and contained 5.0 %w residual alkanol and 1.1 %w polyethylene glycol.
- Another alkoxylation process according to the invention was carried out, in this case using p-toluenesulphonic acid as the second catalyst component.
- About 3.3 grams (0.02 moles) of p-toluene sulphonic acid monohydrate was added to 150 grams (0.773 moles) of predried alkanol reactant and the mixture further dried for 30 minutes under nitrogen sparge at 130 ° C.
- About 2.0 grams (0.01 moles) of aluminium isopropoxide was then added to the mixture and the resulting solution was nitrogen sparged at 130 ° C for an additional 30 minutes to remove isopropanol released by transalcoholysis reaction.
- Ethoxylation was conducted at 170 ° C. A total of 75 grams of ethylene oxide were consumed over a period of 90 minutes. The product was analyzed to have a mean average adduct number of 1.9 and to contain 7.5 %w residual alcohol and 2.5 %w PEG.
- An alkoxylation process according to the invention was carried out using a catalyst containing components which had been pre-mixed, prior to the introduction of the catalyst into the alkanol reactant.
- a catalyst containing components which had been pre-mixed, prior to the introduction of the catalyst into the alkanol reactant.
- 1.0 gram (0.01 mole ) of 95% by weight sulphuric acid was added slowly to 4.93 grams (0.02 moles) of aluminium sec-butoxide (AI(OR) 3 , where R is sec-butyl) at room temperature.
- An exothermic reaction commenced and the -mixture was stirred at 95 °C -for one hour, producing a tight-pink semi-solid product.
- the mixture was then stirred for an additional 16 hours at 25 ° C.
- the pre-mixed catalyst was added at 40 ° C to 300 grams of the pre-dried alkanol reactant. The resulting mixture was heated to 100 °C to dissolve the catalyst and then transferred to the autoclave reactor. The ethoxylation reaction was then conducted in the specified manner, with 116 grams of ethylene oxide consumed over a 100 minute period. Analysis of the product after neutralization indicated a mean average adduct number of 1.7. The product con tained 8.6 %w alcohol and 1.0 %w polyethylene glycol.
- Table III which also illustrates for comparison the distribution obtained for a product of conventional acid (boron trifluoride) catalyzed reaction.
- the product prepared according to the inventive process had a significantly narrower distribution than those of conventional practices.
- This comparative example illustrates that aluminium sulphate is not effective as an alkoxylation catalyst.
- a total of 0.58 grams of aluminium sulphate and 150 grams (0.773 mole) of the dried alkanol reactant were mixed in the autoclave reactor. The mixture was heated to 130 ° C and then contacted with ethylene oxide under a total pressure of 5.2 bar (3.2 bar nitrogen and 2 bar ethylene oxide). No reaction occurred under these conditions. The temperature-of the mixture was increased slowly to 170 ° C and maintained at that temperature with stirring for a total of four hours. No ethylene oxide was consumed, and the alkanol reactant was recovered unchanged.
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Description
- This invention relates to a process for the preparation of an alkanol alkoxylate product having a narrow-range alkylene oxide adduct distribution and a low content of residual alkanol.
- A large variety of products useful, for instance, as nonionic surfactants, wetting and emulsifying agents, solvents, and chemical intermediates, are prepared by the addition reaction (alkoxylation reaction) of alkylene oxides withorganic compounds having one or more active hydrogen atoms. As an example, particular mention may be made of the alkanol ethoxylates and alkyl-substituted phenol ethoxylates prepared by the reaction of ethylene oxide with aliphatic alcohols or substituted phenols of about 6 to 30 carbon atoms. Such ethoxylates, and to a lesser extent corresponding propoxylates and compounds containing mixed oxyethylene and oxypropylene groups, are most commonly applied as nonionic detergent components of commercial cleaning formulations for use in industry and in the home.
-
- The addition of alkylene oxides to alkanols and other active-hydrogen containing compounds is known to be desirably promoted by a catalyst, most conventionally a catalyst of either strongly acidic or strongly basic character. Recognized in the art as suitable basic catalysts are the basic salts of the alkali metals of Group I of the Periodic Table, e.g., sodium, potassium, rubidium, and cesium, and the basic salts of certain of the alkaline earth metals of Group II of the Periodic Table, e.g., calcium, strontium, barium and in some cases magnesium. Conventional acidic alkoxylation catalysts include, broadly, the Lewis acid or Friedel-Crafts catalysts. Specific examples of these catalysts are the fluorides, chlorides, and bromides of boron, antimony, tungsten, iron, nickel, zinc, tin, aluminium, titanium and molybdenum. The use of complexes of such halides with, for example, alcohols, ethers, carboxylic acids, and amines have also been reported. Still other examples of known acidic alkoxylation catalysts are sulphuric and phosphoric acids; perchloric acid and the perchlorates of magnesium, calcium, manganese, nickel and zinc; metal oxalates, sulphates, phosphates, carboxylates and acetates; alkali metal fluoroborates, zinc titanate; and metal salts of benzene sulphonic acid.
- Alkylene oxide addition reactions are known to produce a product mixture of various alkoxylate molecules having different numbers of alkylene oxide adducts (oxyalkylene adducts), e.g., having different values for the adduct number n in formula III above. The adduct number is a factor which in many respects controls the properties of the alkoxylate molecule, and efforts are made to tailor the average adduct number of a product and/or the distribution of adduct numbers within a product to the product's intended service.
- Conventional commercial alkoxylate preparation, which has in large part been limited to the use of basic catalysts, particularly the metals sodium and potassium and their oxides and hydroxides, yields only a relatively broad distribution range product. Conventional acid-catalyzed alkoxylation reactions have long been known to produce a more narrow range product than that obtained with the alkali metal catalysts. Characteristic of the product of the typical acid-catalyzed alkoxylation is a statistical Poisson distribution in which the relative concentration of each individual alkoxylate species may be expressed in terms of the following equation, which is well known to those in the oligomerization and polymerization arts:
- Although acid catalysis provides a relatively narrow distribution product, it is known to have substantial disadvantage in several other respects. For instance, the acids are often unstable with limited life and effectiveness as catalysts in the alkoxylation mixture. Both the acid catalysts themselves and their decomposition products catalyze side reactions producing relatively large amounts of polyalkylene glycols, and also react directly with the components of the alkoxylation mixture to yield undesirable, and often unacceptable, by-products such as organic derivatives of the acid.
- Also of substantial importance in the alkoxylation of the C6 to C30 alkanols is whether the process is able to minimize the quantity of unreacted (or residual) alkanol reactant remaining in the product. A high level of residual alkanol either represents a loss of valuable reactant, or requires that further processing of the product be carried out to recover the alcohol. Moreover, the presence of unreacted alkanol is recognized to be of disadvantage from the standpoint of product quality and enviromental concerns. For instance, residual alkanol in the product contributes to volatile organic emissions during spray drying of detergent formulations.
- It has now been found that certain combinations of (i) one or more sulphur-containing acids and (ii) one or more soluble compounds of aluminium, are very effective as catalysts for the addition reaction of alkylene oxides and C6 to C30 alkanols, and are responsible for alkoxylate products which are characterized by both an exceptionally narrow-range distribution of alkylene oxide adducts and an exceptionally low residual alkanol content.
- Accordingly the invention as defined in the claims, relates to a process for the preparation of an alkanol alkoxylate product having a narrow-range alkylene oxide adduct distribution and a low content of residual alkanol, which is characterised by reacting an alkylene oxide reactant comprising one or more C2 to C4 vicinal alkylene oxides with an alkanol reactant comprising one or more C6 to C30 alkanols in the presence of a catalytically effective amount of a catalyst prepared by contacting (i) one or more sulphur-containing acids selected from the group consisting of sulphur trioxide, sulphuric acid, alkyl sulphuric acids, sulphurous acids, and organic and inorganic sulphonic acids and (ii) one or more aluminium compounds selected from the group consisting of aluminium alcoholates and aluminium phenolates.
- The aluminium alcoholate and/or phenolate compounds can be applied per se, i.e., added directly to the process mixture, or, alternatively, can be formed in situ in the alcohol-containing process mixture by introduction of suitable precursors capable of conversion to aluminium alcoholate and/or phenolate compound(s), which in turn function as a catalyst component or as a precursor to the desired catalyst.
- In comparison to conventional alkoxylation reactions carried out in the presence of conventional acidic catalysts alone, the process of the invention yields (1) a higher quality product relatively free of by-products, (2) a product having a narrower distribution of alkylene oxide adducts, and (3) a product having a reduced level of residual alkanol.
- The invention is applied to processes utilizing an alkylene oxide (epoxide) reactant which comprises one or more C2 to C4 vicinal alkylene oxides. Reactants which comprise ethylene oxide, propylene oxide, or mixtures of ethylene oxide and propylene oxide are preferred, while reactants wherein the alkylene oxide content consists essentially of ethylene oxide are considered particularly preferred.
- The alkanol reactant very suitably comprises one or more alkanols having carbon number in the range from 6 to 30. An alkanol reactant consisting essentially of primary, mono-hydric alkanols is considered most preferred, although secondary and tertiary alcohols as well as polyhydric alkanols are also very suitably utilized in the process of the invention either alone or in mixtures with the primary mono-hydric alkanols. Most preferably, the alkanol reactant consists essentially of one or more C6 to C30 primary mono-hydric alkanols. Preference can also be expressed for alkanols having from 8 to about 20 carbon atoms, with C9 to C18 alkanols considered more preferred and C11 to C16 alcohols considered most preferred. As a general rule, the carbon chains of the alkanols may be of either branched or linear (straight chain) structure, although preference further exists for alkanol reactants in which greater than about 50 per cent, more preferably greater than about 70 per cent and most preferably greater than about 90 per cent of the molecules are of linear (straight-chain) carbon structure. In large part, such preferences relate more to the utility and value of the product alkoxylates in commercial services than to the operability or performance of the process of the invention.
- Commercially available mixtures of primary mono-hydric alkanols prepared via the oligomerization of ethylene and the hydroformylation or oxidation and hydrolysis of the resulting higher olefins are particularly preferred. Examples of such commercially available alkanol mixtures include the NEODOL Alcohols, trademark of and sold by Shell Chemical Company, including mixtures of C9, C10 and C11 alkanols (NEODOL 91), mixtures of C12 and C13 alkanols (NEODOL 23), mixtures of C12, C13, C14, and Cis alkanols (NEODOL 25), and mixtures of C14 and Cis alkanols (NEODOL 45); the ALFOL Alcohols, trademark of and sold by Continental Oil Co., including mixtures of C10 and C12 alkanols (ALFOL 1012), mixtures of C12 and C14 alkanols (ALFOL 1214), mixtures of C16 and C18 alkanols (ALFOL 1618), and mixtures of C16, C18 and C20 alkanols (ALFOL 1620); the EPAL Alcohols, trademark of and sold by Ethyl Chemical Company, including mixtures of C10 and C12 alkanols (EPAL 1012), mixtures of C12 and C14 alkanols (EPAL 1214), and mixtures of C14, C16, and C18 alkanols (EPAL 1418); and the TERGITOL-L Alcohols, trademark of and sold by Union Carbide Corporation, including mixtures of C12, C13, C14, and C15 alkanols (TERGITOL-L 125). Also very suitable are the commercially available alkanols prepared by the reduction of naturally occuring fatty esters.
- For purposes of the invention, the alkylene oxide reactant and the active hydrogen reactant are necessarily contacted in the presence of the specified two-component catalyst.
- As one component of this catalyst, the process of the invention makes use of one or more sulphur-containing acids sclected from sulphur trioxide (S03) and acids of the class represented by the empirical formula ZSO3H. Included within this class are sulphuric acid (with Z in the formula representing -OH), monoalkyl esters of sulphuric acid which are also commonly called alkyl sulphuric acids (with Z representing an alkoxy group), sulphurous acid (wherein Z represents H), and sulphonic acids wherein Z represents a univalent inorganic atom or organic radical.
- Preferred alkyl sulphuric acids include those with an alkoxy group of about 1 to 30 carbon atoms. Alkyl sulphuric acids having an alkoxy group of about 1 to 20 carbon atoms are more preferred, while those having an alkoxy group of about 8 to 20 carbon atoms are considered most preferred.
- Specific examples of suitable inorganic sulphonic acids include chlorosulphonic acid (wherein Z is CI), fluorosulphonic acid-(wherein Z is F) and sulphamic acid (wherein Z is NH2).
- Suitable organic sulphonic acids include the alkane- and cycloalkane sulphonic acids, as well as arenesulphonic acids and heterocyclic sulphonic acids. Specific examples of the alkane sulphonic acids include methanesulphonic acid, ethanesulphonic acid, propanesulphonic acid, butanesulphonic acid, pen- tanesulphonic acid, hexanesulphonic acid, dodecanesulphonic acid, hexadecanesulphonic acid, trifluoromethane sulphonic acid, sulphosuccinic acic, and cyclohexylsulphonic acid. Specific examples of arenesulphonic acids include benzenesulphonic acid, toluenesulphonic acid, styrene-(i.e., vinyl benzene) sulphonic acid, 5-sulphosalicylic acid, phenolsulphonic acid, and 1,6-napthalene disulphonic acid. Specific examples of heterocyclic sulphonic acids include sulphanilic acid. Alkyl and aryl groups of the sulphonic acid molecule are suitable substituted with relatively inert organic and/or inorganic substituents. Examples of substituted organic sulphonic acids include 4-hydroxybenzoic acid, trifluoromethane sulphonic acid, isethionic acid, and taurine.
- As is the case for the aluminium containing component of the catalyst, the sulphur-containing catalyst component is suitably introduced directly to the process mixture or formed therein upon addition to the mixture of precursors of the sulphur-containing acid(s). Mixtures of sulphur-containing acids are very suitable.
- A particularly preferred group of sulphur-containing acids is that which consists of sulphuric acid, sulphur trioxide, C1 to C30 alkyl sulphuric acids, sulphanilic acid, toluenesulphonic acid, styrenesulphonic acid, methanesulphonic acid, and 5-sulphosalicylic acid. A catalyst component selected from the group consisting of sulphuric acid, sulphur trioxide, and the C1 to C30 alkyl sulphuric acids is considered more preferred, and sulphuric acid is considered most preferred, for use in the invention from the standpoint of overall process performance and economics, and of product quality.
- The second necessary component of the catalyst of the process of the invention suitably comprises one or more aluminium alcoholate ore phenolate compounds. Preferably, this component comprises one or more alkoxide or phenoxide compounds of the formula
- Specific examples of preferred alkoxide compounds suitable as catalyst components for purposes of the invention include the aluminium alkoxides (wherein R is C1 to C30 alkyl), including the lower alkoxides, e.g., aluminium ethoxide, aluminium isopropoxide, and aluminium t-butoxide, as well as the higher alkoxides having one or more of their alkyl R substituents in the same Ca to C20 range as the alkanol reactant of the process, e.g., nonyl, decyl, dodecyl, and hexadecyl groups. Specific examples of preferred phenoxide compounds useful in this service include aluminium phenoxide, lower alkyl-substituted phenol derivatives such as aluminium benzyloxide and higher alkyl-substituted phenol derivatives, e.g., compounds wherein R represents nonylphenyl, tridecylphenyl, pentadecylphenyl, etc. Specific examples of preferred compounds which serve as precursors for the formation in situ of aluminium alkoxide compounds include aluminium triacetate and trialkylaluminium compounds such as trimethylaluminium and triethylaluminium.
- Particular preference exists for the use of an alkoxide in which each of the Xl, X2, and X3 substituents is an -OR group wherein R is an alkyl group having a carbon number in the range from 1 to 30, more preferably a carbon number in the range from 1 to 20, and most preferably a carbon number which corresponds to the carbon number(s) of the particular alkanol reactant employed in the given process application. Thus, for instance, the reaction of a dodecyl alcohol reactant is most preferably conducted in the presence of a catalyst which comprises a catalyst in which a substantial portion of the second catalyst component is a compound of the formula Al-(OR)3, wherein each R is a dodecyl group. Without intention that the invention be limited to one theory or mechanism of operation, it is thought that the alcoholate and phenolate compounds commonly undergo transalcoholysis reactions in the presence of the alkanol reactant and are converted, at least in part, to alkoxides having alkyl substituents of carbon numbers which correspond to those of the alkanol reactant. Thus, for example, when an aluminium isopropoxide catalyst component is contacted with a higher alkanol alkoxylation reactant (e.g., a G2 to C15 alkanol mixture) a transalcoholysis reaction results which liberates isopropanol and converts at least a portion of the aluminium isopropoxide to aluminium alkoxides having Cn to C15 alkyl substituents. In one preferred embodiment of the invention, a lower carbon number aluminium alkoxide (e.g., an alkoxide characterized by alkyl group carbon number(s) of less than about 6) is mixed with the alkanol reactant, prior to contact with the alkylene oxide reactant, under conditions which favour the conversion by transalcoholysis of the lower alkoxide compounds to alkoxide compounds which correspond in carbon number (or carbon number distribution) of the alkoxide substituent to the carbon number (or carbon number distribution) of the alkanol reactant.
- In the practice of the process of the invention, the catalyst components are preferably applied in a molar ratio of the first sulphur-containing acid component to the second aluminium containing component that is in the range from 0.1:1 to 2:1. Higher relative ratios result in lower reaction rates and higher degrees of by-product formation, while at lower ratios the reaction rate is undesirably low. Molar ratios of the first catalyst component to its second component in the range from 0.3:1 to 1:1 are more preferred, while molar ratios between 0.4:1 and 0.6:1 are considered most preferred.
- The catalyst combination is present in the reaction mixture in a catalytically effective amount. For the typical practical operation, a quantity of catalyst is desirably at least about 0.01 %w (per cent by weight) of the combined total of the two components relative to the alkanol reactant. Although catalyst quantity is not narrowly critical, preference may be expressed for use of the catalyst in amount of at least about 0.05 %w, while an amount between 0.1 and 1 %w is considered most preferred. Substantially greater quantities of catalyst, e.g., up to 10 %w, are also very suitable.
- In terms of processing procedures, the alkoxylation reaction in the invention may be conducted in a generally conventional manner. For example, the catalyst components may initially be mixed with the alkanol reactant. A substantially liquid mixture forms, although it is not necessary that all of the added catalyst dissolve in the alkanol. This mixture is then contacted, preferably under agitation, with alkylene oxide reactant, which is typically introduced in gaseous form.
- The order in which the catalyst components and the reactants are contacted has not been found to be critically important to the invention. Thus, for instance, it is suitable practice to premix the aluminium compound catalyst component with the sulphur-containing component, prior to their introduction into contact with the alkanol reactant. The observation of a reaction between the two catalyst components when they are pre-mixed in the absence of alcohol and ethylene oxide suggests that the two specified components may in fact serve as precursors of a single effective catalyst which has not been otherwise identified. Accordingly, the catalyst is described with reference to a combination of, or, equivalently, to a catalyst prepared by contacting the two specified components.
- Also very suitable, and generally preferred from the standpoint of convenience, is a combination of the two components by contact in the presence of the alkanol reactant, e.g., by independent, addition of the two components to the reactant.
- It is considered surprising that such mixing or premixing of the two components results in an active catalyst for the alkoxylation reaction, in view of observations that aluminium sulphate salt is not effective as a catalyst for the desired reaction.
- Overall, the two reactants are utilized in quantities which are predetermined to yield an alkoxylate product of the desired mean or average adduct number, e.g., typically from less than one to about 30. In general terms, suitable and preferred process temperatures are from 70 °C to 200 °C and pressures above atmospheric pressure are preferred. A temperature of at least about 70 °C, particularly at least 100 °C, is typically preferred for a significant rate of reaction, while a temperature less than 200 °C, particularly less than 180 °C, and most particularly less than 170 °C, is typically desirable to minimize degradation of the product. The two-component catalyst used in the invention is highly active, and care must be taken to control the temperature of the exothermic reaction. Superatmospheric pressures, e.g., pressures between 0.7 and 11 bar (gauge) are preferred. While these procedures describe a batch mode of operation, the invention is equally applicable to a continuous process.
- The alkanol reactant is generally a liquid and the alkylene oxide reactant is generally a vapour for such reactions. Alkoxylation is then suitably conducted by introducing gaseous alkylene oxide into a pressure reactor containing the liquid alkanol and the two components of the catalyst combination. For considerations of process safety, the partial pressure of the lower alkylene oxide reactant is preferably limited, for instance, to less than about 4 bar and/or the reactant is preferably diluted with an inert gas such as nitrogen, for instance, to a vapour phase concentration of about 50 per cent or less. The reaction can, however, be safely accomplished at greater alkylene oxide concentration, greater total pressure and greater partial pressure of alkylene oxide if suitable precautions, known to the art, are taken to manage the risks of explosion. A total pressure of between 3 and 8 bar (gauge) with an alkylene oxide partial pressure between 1 and 4 bar (gauge), is particularly preferred, while a total pressure of between 3.5 and 6.5 bar (gauge) with an alkylene oxide partial pressure between 1.5 and 3.5 bar (gauge), is considered more preferred.
- After the ethoxylation reaction has been completed, the product is preferably neutralized to deactivate the catalyst. Neutralization is suitably accomplished by the addition of a base such as sodium or potassium hydroxide to the acidic product mixture. Neutralized catalyst residues are very suitably left in the product, or may be removed if desired, for example, by precipitation or extraction or the like.
- The alkoxylate prepared in the process of the invention is typically a product of very acceptable quality, having a relatively low content of polyalkylene glycols and other by-products, as well as a low content of residual alkanol reactant. Although the content of residual alkanol will vary from one alkoxylation product to another, and is dependent upon the degree of alkoxylation, i.e., the average alkylene oxide adduct number, the residual alkanol content of a product prepared according to the invention and having a given average adduct number is less than the content of residual alkanol in a product of like average adduct number which has been prepared according to conventional acid-catalyzed alkoxylation.
- Except as noted otherwise, each of the Examples and Comparative Examples were conducted under the following procedure. All alkoxylation reactions were conducted in a one-litre stainless steel autoclave reactor. In each case, the alkylene oxide reactant consisted of ethylene oxide and the alkanol reactant was a NEODOL 23 Alcohol (trademark of Shell Chemical Company) characterized as a mixture of primary, 80% linear (20% branched) alkanols having twelve and thirteen carbon atoms (about 40% by mole C12 and 60% by mole C13). Initially, the liquid alkanol reactant was dried to a water content of about 40 ppm (as indicated by Karl Fischer water analysis) by sparging with nitrogen at 130 °C for one hour. About 2.0 grams (0.01 moles) of the first (aluminium compound) catalyst component was dissolved in about 150 grams (0.773 moles) of the dried alkanol in a multineck glass round-bottom flask at 100 °C. The reaction mixture was cooled to about 30 °C at which point about 0.5 grams (0.005 moles) of the second (sulphur-containing acid) component was dissolved in the alkanol solution, producing a clear, colourless solution. This solution was transferred to the autoclave under a nitrogen atmosphere, and the reactor sealed and heated to 120 °C. A mixture of nitrogen and ethylene oxide was then introduced into the reactor to a total pressure of 5.2 bar (3.2 bar nitrogen and 2 bar ethylene oxide). Alkoxylation (ethoxylation) commenced immediately. Temperature of the exothermic reaction mixture was allowed to rise to 140 °C and cooling was then applied to the reactor to maintain that temperature. Ethylene oxide was added to the reactor on demand, that is, at a rate necessary to maintain approximately constant pressure. Sufficient ethylene oxide was added to the reactor to produce a product having the desired average ethylene oxide adduct number. Ethylene oxide introduction was then discontinued and the reactor was maintained at 140 °C for an additional hour, to substantially consume unreacted ethylene oxide in the system. At the end of this hour, the reactor was cooled to 90 °C, and the product was transferred under nitrogen atmosphere to a sample bottle and neutralized with base (i.e., potassium hydroxide) to a pH of about 6.5. The product was analyzed by GC-LC techniques to determine the mean average adduct number of the ethoxylate, the ethylene oxide adduct distribution of the ethoxylate, the content of residual alkanol reactant in the product, and the quantity of polyethylene glycol by-products formed.
- Example 1 followed the general procedures outlined above, utilizing aluminium isopropoxide (AI(OR)3, where R is isopropyl) as the first catalyst component and concentrated (96%) sulphuric acid as the second catalyst component. For purposes of the alkoxylation, 75 grams (2.2 moles) of ethylene oxide was added to the autoclave over a period of 30 minutes.
- The alkanol ethoxylate product was found to have a mean average adduct number of 2.0 and to contain 4.4 %w of residual alkanol reactant. The product also contained 0.6 %w polyethylene glycols (PEG).
- The ethylene oxide adduct distribution of the product is presented in Table I and compared with that of (1) an ethoxylate of equivalent mean adduct number which was produced using a conven tional potassium hydroxide catalyst and (2) with a (calculated) Poisson distribution as is characteristic of conventional acid-catalyzed ethoxylation reactions. The distribution is substantially more narrow than that which is characteristic of conventional base-catalyzed ethoxylation reactions, including those catalyzed by compounds of sodium or potassium or other Group I metals as well as those catalyzed by compounds of barium or other Group II metals. Moreover, the distribution is more narrow than that obtained using conventional acid catalysts such as sulphuric acid.
- For Example 2, the general procedures were again followed as in Example 1, with the addition of separate processing step for the conversion of substantially all of the aluminium isopropoxide to an aluminium alkoxide of the CJ2 and C13 alkanols. After the addition of the second (sulphuric acid) catalyst component to the 150 grams of the dried alkanol reactant, and before the transfer of the alkanol/catalyst mixture to the autoclave, the mixture was heated to 130 °C and maintained at this temperature under a nitrogen sparge for two hours. Under these conditions, a transalcoholysis reaction occurred between the aluminium isopropoxide and the C12 and C13 alkanols. Isopropanol released by alcoholysis was removed from the system by the nitrogen sparge. Following the transalcoholysis, the mixture was cooled to 30 °C and transferred to the autoclave under nitrogen atmosphere.
- A total of 76 grams of ethylene oxide was added to the reactor during the ethoxylation reaction, over a period of 60 minutes. The product was determined to have a mean average adduct number of 2.4, and to contain 3.1 %w residual alcohol and 0.5% PEG. Ethylene oxide adduct distribution was also determined and is presented in the Table II, together with a comparative Poisson distribution.
- An alkoxylation process according to the invention was carried out using aluminium t-butoxide (AI(OR)3, where R is t-butyl) as the first catalyst component. In this Example 3, about 5.0 grams (0.02 moles) of aluminium t-butoxide was dissolved in about 300 grams (1.55 moles) of the dried alkanol reactant at 100 °C. The mixture was cooled to 30 °C and about 1.0 gram (0.01 moles) of concentrated sulphuric acid was added, producing a slightly hazy, colourless solution. The general procedure was then again followed for the ethoxylation reaction.
- A total of 150 grams of ethylene oxide was consumed over a 90 minute reaction at 140 °C. Analysis of the neutralized product indicated an alkoxylate with a mean average adduct number of 2.1, containing 4.5 %w residual alkanol and 1.8 %w PEG. The ethylene oxide distribution of the product was similar to that obtained in Example 1.
- An alkoxylation process according to the invention was conducted using a catalyst which contained the two catalyst components in a molar ratio of 1:1, i.e., one part of the first component (aluminium isopropoxide) and one part of the second component (concentrated sulphuric acid). For this purpose, about 1.1 grams (0.005 moles) of the first component was dissolved in 150 grams of the predried alkanol reactant at 100 °C. The mixture was then cooled to 30 °C, and about 0.5 grams (0.005 moles) of the sulphuric acid was added.
- A total of about 70 grams of ethylene oxide was consumed over a period of 120 minutes. The product had a mean average adduct number of 2.0, and contained 4.4 %w residual alkanol and 2.1 %w PEG.
- For Example 5, sulphur trioxide was utilized as the second catalyst component. About 2.7 grams (0.013 moles) of aluminium isopropoxide was dissolved in the 150 grams of alkanol reactant at 100 °C. The mixture was cooled to 30 °C, and 1.06 grams (0.013 moles) of sulphur trioxide was added.
- A total of 75 grams of ethylene oxide was consumed over a 30 minute ethoxylation reaction. Alkoxylate product had a mean average adduct number of 2.3, and contained 5.0 %w residual alkanol and 1.1 %w polyethylene glycol.
- Another alkoxylation process according to the invention was carried out, in this case using p-toluenesulphonic acid as the second catalyst component. About 3.3 grams (0.02 moles) of p-toluene sulphonic acid monohydrate was added to 150 grams (0.773 moles) of predried alkanol reactant and the mixture further dried for 30 minutes under nitrogen sparge at 130 °C. About 2.0 grams (0.01 moles) of aluminium isopropoxide was then added to the mixture and the resulting solution was nitrogen sparged at 130 °C for an additional 30 minutes to remove isopropanol released by transalcoholysis reaction.
- Ethoxylation was conducted at 170 °C. A total of 75 grams of ethylene oxide were consumed over a period of 90 minutes. The product was analyzed to have a mean average adduct number of 1.9 and to contain 7.5 %w residual alcohol and 2.5 %w PEG.
- An alkoxylation process according to the invention was carried out using a catalyst containing components which had been pre-mixed, prior to the introduction of the catalyst into the alkanol reactant. For this purpose, 1.0 gram (0.01 mole ) of 95% by weight sulphuric acid was added slowly to 4.93 grams (0.02 moles) of aluminium sec-butoxide (AI(OR)3, where R is sec-butyl) at room temperature. An exothermic reaction commenced and the -mixture was stirred at 95 °C -for one hour, producing a tight-pink semi-solid product. The mixture was then stirred for an additional 16 hours at 25 °C.
- The pre-mixed catalyst was added at 40 °C to 300 grams of the pre-dried alkanol reactant. The resulting mixture was heated to 100 °C to dissolve the catalyst and then transferred to the autoclave reactor. The ethoxylation reaction was then conducted in the specified manner, with 116 grams of ethylene oxide consumed over a 100 minute period. Analysis of the product after neutralization indicated a mean average adduct number of 1.7. The product con tained 8.6 %w alcohol and 1.0 %w polyethylene glycol. The ethoxylate distribution of the product prepared by the process of this Example is presented in Table III, which also illustrates for comparison the distribution obtained for a product of conventional acid (boron trifluoride) catalyzed reaction. The product prepared according to the inventive process had a significantly narrower distribution than those of conventional practices.
- An alkoxylation process was conducted under the general procedures outlined above, but in the absence of the first catalyst component (the aluminium compound), and thus not in accordance with the invention. The only catalyst employed in this experiment was a sulphur-containing acid, in particular, sulphuric acid.
- About 0.5 grams (0.005 moles) of sulphuric acid was dissolved in 150 grams (0.773 moles) of predried alkanol at 30 °C. (no aluminium compound was added to this mixture.) The solution was transferred to the reactor and contacted with ethylene oxide under the general procedures. No reaction was observed at 140 °C. As the reactor temperature was slowly increased, alkoxylation commenced at about 160 °C to 170 °C. About 57 grams of ethylene oxide was consumed over a four hour period. The product had a mean average adduct number of about 1.0 and was found to contain 5.8 %w PEG and a substantial quantity of other by-products which were not identified. The nature and quantity of the by-products did not permit determination of the ethoxylate distribution.
- An alkoxylation process was conducted under the same general procedures, but in the absence of the second catalyst component (the sulphur-containing acid). In other words, the process was carried out in the presence of aluminium isopropoxide, but in the absence of a sulphur-containing acid.
- About 1.0 gram (0.005 mole) of aluminium isopropoxide was mixed with 68 grams (0.35 mole) of the dried alkanol reactant. The mixture was sparged with nitrogen for 30 minutes at 130 °C and then transferred to a 300 millilitre stainless autoclave reactor and heated to 170 °C. Ethylene oxide and nitrogen were charged to the reactor to bring the total pressure to 5.9 bar (3.9 bar nitrogen and 2 bar ethylene oxide). Ethoxylation commenced, but was extremely slow-only 12.3 grams of ethylene oxide were consumed over a five hour period. Analysis of the product indicated the formation of an alkoxide with a mean average adduct number of 0.9 and a residual alkanol content of 37.4 %w.
- This comparative example illustrates that aluminium sulphate is not effective as an alkoxylation catalyst. A total of 0.58 grams of aluminium sulphate and 150 grams (0.773 mole) of the dried alkanol reactant were mixed in the autoclave reactor. The mixture was heated to 130 °C and then contacted with ethylene oxide under a total pressure of 5.2 bar (3.2 bar nitrogen and 2 bar ethylene oxide). No reaction occurred under these conditions. The temperature-of the mixture was increased slowly to 170 °C and maintained at that temperature with stirring for a total of four hours. No ethylene oxide was consumed, and the alkanol reactant was recovered unchanged.
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US4721817A (en) * | 1986-12-31 | 1988-01-26 | Shell Oil Company | Preparation of nonionic surfactants |
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DE3814849A1 (en) * | 1988-05-02 | 1989-11-16 | Henkel Kgaa | USE OF ESTERS OF TITANIC AND / OR ZIRCONIC ACIDS AS CATALYSTS FOR ETHOXYLATION OR. PROPOXYLATION |
US4933502A (en) * | 1988-06-02 | 1990-06-12 | Shell Oil Company | Process for the preparation of nonionic surfactants |
CA1339903C (en) * | 1988-08-09 | 1998-06-09 | Eugene Frederick Lutz | Process for the preparation of surfactants having improved physical properties |
US5118650A (en) * | 1988-09-30 | 1992-06-02 | Union Carbide Chemicals & Plastics Technology Corporation | Alkoxylation using modified group iiib metal-containing bimetallic or polymetallic catalysts |
US5112789A (en) * | 1988-09-30 | 1992-05-12 | Union Carbide Chemicals & Plastics Technology Corporation | Alkoxylation catalysis |
US5114900A (en) * | 1988-09-30 | 1992-05-19 | Union Carbide Chemicals & Plastics Technology Corporation | Alkoxylation using modified calcium-containing bimetallic or polymetallic catalysts |
US5120697A (en) * | 1988-09-30 | 1992-06-09 | Union Carbide Chemicals & Plastics Technology Corporation | Alkoxylation using modified calcium-containing catalysts |
US5112788A (en) * | 1988-09-30 | 1992-05-12 | Union Carbide Chemicals & Plastics Technology Corporation | Alkoxylation using modified group iia metal-containing bimetallic or polymetallic catalysts |
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-
1985
- 1985-12-23 US US06/812,604 patent/US4721816A/en not_active Expired - Lifetime
-
1986
- 1986-12-08 DE DE8686202215T patent/DE3669498D1/en not_active Expired - Fee Related
- 1986-12-08 ES ES86202215T patent/ES2014415B3/en not_active Expired - Lifetime
- 1986-12-08 EP EP86202215A patent/EP0228121B1/en not_active Expired - Lifetime
- 1986-12-12 ZA ZA869385A patent/ZA869385B/en unknown
- 1986-12-15 CA CA000525295A patent/CA1270495A/en not_active Expired - Fee Related
- 1986-12-22 AU AU66839/86A patent/AU592139B2/en not_active Ceased
- 1986-12-22 NZ NZ218744A patent/NZ218744A/en unknown
- 1986-12-23 JP JP61305625A patent/JPS62164641A/en active Pending
Also Published As
Publication number | Publication date |
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AU592139B2 (en) | 1990-01-04 |
DE3669498D1 (en) | 1990-04-19 |
AU6683986A (en) | 1987-06-25 |
NZ218744A (en) | 1989-06-28 |
ZA869385B (en) | 1987-07-29 |
EP0228121A1 (en) | 1987-07-08 |
JPS62164641A (en) | 1987-07-21 |
CA1270495A (en) | 1990-06-19 |
ES2014415B3 (en) | 1990-07-16 |
US4721816A (en) | 1988-01-26 |
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